EP1210294B1 - HOCHGEFÜLLTE SiO2-DISPERSION, VERFAHREN ZU IHRER HERSTELLUNG UND VERWENDUNG - Google Patents

HOCHGEFÜLLTE SiO2-DISPERSION, VERFAHREN ZU IHRER HERSTELLUNG UND VERWENDUNG Download PDF

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EP1210294B1
EP1210294B1 EP00965941A EP00965941A EP1210294B1 EP 1210294 B1 EP1210294 B1 EP 1210294B1 EP 00965941 A EP00965941 A EP 00965941A EP 00965941 A EP00965941 A EP 00965941A EP 1210294 B1 EP1210294 B1 EP 1210294B1
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Prior art keywords
sio
particles
dispersion
amorphous
pore diameter
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German (de)
English (en)
French (fr)
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EP1210294A1 (de
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Fritz Schwertfeger
Johann Weis
Peter Ritter
Achim Molter
Wolfgang Schweren
Volker Frey
Hans-Peter Scherm
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Wacker Chemie AG
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Wacker Chemie AG
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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Definitions

  • the invention relates to highly filled SiO 2 dispersions, to processes for their preparation and to processes for producing porous amorphous SiO 2 shaped bodies with extremely high degrees of filling from the dispersion, these shaped bodies and their preparation.
  • Porous, amorphous SiO 2 shaped bodies are used in many technical fields. Examples include filter materials, thermal insulation materials or heat shields.
  • quartz goods of all types can be produced from amorphous, porous SiO 2 shaped bodies by means of sintering and / or melting.
  • Highly pure porous SiO 2 shaped bodies can serve, for example, as "preform" for glass fibers or optical fibers.
  • crucibles for pulling silicon single crystals can also be produced in this way.
  • porous moldings Regardless of the use of porous moldings one is always endeavoring to produce as close as possible to a near-net shape. That is, in the course of the production of the molding Only little or no shrinkage should occur.
  • Porous SiO 2 shaped bodies can in principle be produced by pressing corresponding SiO 2 powders or by a wet chemical process.
  • porous SiO 2 shaped bodies The preferred way to prepare porous SiO 2 shaped bodies is therefore the wet chemical route.
  • sol-gel process This generally starts from sol-containing silicon-containing monomers (sol), which form a nanoporous three-dimensional SiO 2 network (gel) by means of hydrolysis and / or polycondensation.
  • sol-containing silicon-containing monomers sol-containing silicon-containing monomers
  • gel nanoporous three-dimensional SiO 2 network
  • subcritical or supercritical drying of the porous shaped body is then obtained.
  • gels with a solids content of about 10-20 wt.% Can be obtained.
  • an extremely high shrinkage occurs, which means that moldings close to final contours can not be produced reproducibly.
  • the shaped body does not shrink, but it then only has a solids content of 10-20% by weight.
  • EP 318100 Another method is described in EP 318100. It will a dispersion of fumed silica, prepared with particles in the size range of 10-500 nm in water. After shaping and solidification of the dispersion by means of Drying of the corresponding moldings obtained. It receives one solid contents of up to 60 wt.%.
  • EP 653381 and DE-OS 2218766 disclose a slip casting process in which a dispersion of quartz glass particles with a Particle size of 0.45 to 70 microns, preferably 1-10 microns in Water is produced.
  • the achievable solids content of Dispersion is between 78 and 79% by weight.
  • the dispersion is subsequently in a porous form by slow removal of water solidified and dried after demolding.
  • the slip casting process is due to the Diffusion-dependent dehydration very time-consuming and only applicable for thin-walled moldings.
  • the solidification leads by removal of water by means of porous forms to an undesirable Density gradients within the molding, what in the later sintering, both different sintering temperatures, Sintering times and density differences causes.
  • dispersions must be realized with extremely high solids content. This leads to great problems in practice, since dispersed SiO 2 particles cause a strong thixotropic effect. During dispersing, a dilatant phase occurs. This is noticeable in that the viscosity of the suspension increases with increasing shear. In order to achieve a still pourable, but highly filled dispersion, it requires a complex process with a change of low shear during stirring and high shear during homogenization. Because of the very rapid solidification of such a highly filled suspension, it is also difficult to realize a homogeneous shaping of the dispersion.
  • a composition for the production of silica glass is known, the fumed silica having an average particle diameter of 5x10 -3 to 1x10 -1 microns and a specific surface area of 50 to 400m 2 / g and heat-treated silica, as an agglomerate a fumed silica having a mean diameter of 2 to 15 microns and a lower specific surface area than the fumed silica, plasticizer (eg, tetramethylammonium hydroxide), dispersing agent (eg, polyethyloxazoline, glycerin), and binder (eg, methyl formate).
  • plasticizer eg, tetramethylammonium hydroxide
  • dispersing agent eg, polyethyloxazoline, glycerin
  • binder eg, methyl formate
  • Such a composition is wholly unsuitable for the production of highly pure sintered bodies due to its content of different organic and / or inorganic additives.
  • only fill levels of up to 51% by weight solids are achieved in the disclosed compositions and resulting green bodies.
  • a process for the production of amorphous SiO 2 moldings which have a degree of filling of up to 80% by weight.
  • This SiO 2 particles are used with an average particle diameter of 0.1 to 100 .mu.m.
  • the particles In order to be able to achieve such high filling levels at all, the particles must be dispersed in basic water (pH> 10, eg by means of TMAH) by means of large and lengthy shear stress (eg ball mill). Due to the unavoidable impurities resulting from the use of bases and the abrasion (abrasive behavior of the SiO 2 particles) during the long and intensive shearing, such a composition is wholly unsuitable for producing high-purity SiO 2 shaped bodies.
  • US Pat. No. 4,929,579 discloses a method by which fumed silica articles are produced using a dispersion, this dispersion containing amorphous SiO 2 particles having a trimodal particle size distribution.
  • a dispersion is very complicated to produce.
  • very large particles average particle diameter> 300 .mu.m
  • inhomogeneities and sedimentation phenomena occur in the dispersion.
  • there are density fluctuations within the dispersion or the shaped bodies which leads to considerable difficulties with regard to dimensional accuracy and isotropic shrinkage in subsequent shaping processes and sintering.
  • An object of the present invention was to provide a highly filled, homogeneous and highly pourable dispersion with SiO 2 particles which does not have the disadvantages known from the prior art.
  • a homogeneous dispersion of amorphous SiO 2 particles in a dispersion medium characterized in that the dispersion has a degree of filling of at least 80 wt.% Of amorphous SiO 2 particles and the amorphous SiO 2 particles formed a bimodal particle size distribution of larger round amorphous SiO 2 particles and smaller round amorphous SiO 2 particles, and water as a dispersant, which has a resistance of ⁇ 18 MegaOhm * cm.
  • the dispersion preferably has a degree of filling of at least 83% by weight of amorphous SiO 2 particles.
  • the dispersion particularly preferably has a degree of filling of at least 86% by weight of amorphous SiO 2 particles.
  • a mineral acid such as HCl, HF, H 3 PO 4 , H 2 SO 4 or silica or ionogenic additives such as fluorine salts is added to the water.
  • HCl or HF particularly preferably HF.
  • a pH of 2-7, preferably 3-5 should be set in the dispersion.
  • a mineral base may be added to the water, such as NH 3 , NaOH or KOH. Particularly preferred is NH 3 and NaOH, most preferably NH 3 . However, it is also possible to use mixtures of the compounds mentioned. In this case, a pH of 7-11, preferably 9-10 should be set.
  • the reduction or increase in the pH leads to a Reduction of thixotropy, so that reaches a higher degree of filling can be and the dispersion more fluid and easier is malleable.
  • the amorphous SiO 2 particles have a round, ie spherical and compact morphology, as can be seen for example in FIG.
  • the larger amorphous SiO 2 particles preferably have a particle size distribution with a D 50 value between 1-200 ⁇ m, preferably between 1-100 ⁇ m, particularly preferably between 10-50 ⁇ m and very particularly preferably between 10-30 ⁇ m. Furthermore, the narrowest possible particle distribution is advantageous.
  • amorphous SiO 2 particles having a BET surface area of 0.001 m 2 / g - 50 m 2 / g, particularly preferably from 0.001 m 2 / g - 5m 2 / g, most preferably from 0.01 m 2 / g - 0.5 m 2 / g.
  • the bimodal particle size distributions are obtained by admixing with amorphous SiO 2 particles, such as fused or fumed silica with a particle size of 1-400 nm, preferably 10 to 200 nm, and particularly preferably 50 to 130 nm, in an amount of 0.1 to 50% by weight, based on the total solids content of the dispersion, more preferably in an amount of from 1 to 30% by weight, very particularly preferably in an amount of from 1 to 10% by weight.
  • amorphous SiO 2 particles such as fused or fumed silica with a particle size of 1-400 nm, preferably 10 to 200 nm, and particularly preferably 50 to 130 nm, in an amount of 0.1 to 50% by weight, based on the total solids content of the dispersion, more preferably in an amount of from 1 to 30% by weight, very particularly preferably in an amount of from 1 to 10% by weight.
  • amorphous SiO 2 particles preferably have a BET surface area between 30 and 400 m 2 / g, more preferably between 130 and 300 m 2 / g.
  • nanoscale amorphous SiO 2 particles act as a kind of inorganic binder between the much larger SiO 2 particles, but not as a filler material to achieve a much higher degree of filling. They cause that in the production of stable moldings can be dispensed with a dehydration substantially. Furthermore, they influence the viscosity or the plastic behavior of the dispersion.
  • the specific gravity of the amorphous SiO 2 particles should preferably be between 1.0 and 2.2 g / cm 3 . More preferably, the particles have a specific gravity between 1.8 and 2.2 g / cm 3 . Most preferably, the particles have a specific gravity between 2.0 and 2.2 g / cm 3 .
  • amorphous SiO 2 particles having ⁇ 3 OH groups per nm 2 on their outer surface, particularly preferably ⁇ 2 OH groups per nm 2 , and very particularly preferably ⁇ 1 OH groups per nm 2 .
  • the amorphous SiO 2 particles should preferably have a crystalline content of at most 1%. Preferably, they should also show the least possible interaction with the dispersant.
  • amorphous SiO 2 particles of different origin such as fused silica, as well as any type of amorphous sintered or compacted SiO 2 . They are therefore preferably suitable for the preparation of the dispersion according to the invention.
  • Corresponding material can be in a conventional manner and Make way in the oxyhydrogen flame. It is also for sale available, e.g. under the name Excelica® at Tokoyama, Japan.
  • particles of others can also be used Origin, such as e.g. Natural quartz, quartz glass sand, glassy silica, ground quartz glass or ground Quartz glass waste and chemically produced silica glass, such as. precipitated silica, fumed silica (Fumed Silica, prepared by means of flame pyrolysis), xerogels, or Aerogels.
  • Origin such as e.g. Natural quartz, quartz glass sand, glassy silica, ground quartz glass or ground Quartz glass waste and chemically produced silica glass, such as. precipitated silica, fumed silica (Fumed Silica, prepared by means of flame pyrolysis), xerogels, or Aerogels.
  • the larger amorphous SiO 2 particles are preferably precipitated silicas, finely divided silicas, fused silica or compacted SiO 2 particles, more preferably highly dispersed silicic acid or fused silica, very particularly preferably fused silica. Mixtures of the mentioned different SiO 2 particles are likewise possible and preferred.
  • the particles described above are present in a highly pure form, ie with a foreign atom content, in particular of metals ⁇ 300 ppmw (parts per million by weight), preferably ⁇ 100 ppmw, more preferably ⁇ 10 ppmw and most preferably ⁇ 1 ppmw ,
  • additives such as glass fiber, glass breakage, glass particles can also be added to the dispersion.
  • silica glass fibers are added.
  • the dispersion additionally metal particles, metal compounds or metal salts contain.
  • Preferred compounds are those in the dispersion medium are soluble, particularly preferred are water-soluble Metal salts.
  • the additives metal particles, metal compounds or metal salts may during and / or after the preparation of the dispersion be added.
  • the invention further relates to a process which allows a preparation of the dispersion according to the invention in a very simple manner.
  • the process according to the invention is characterized in that amorphous SiO 2 particles having a round and compact form are incorporated into a dispersion medium initially introduced. The formation of a dilatant behavior should be largely suppressed.
  • the formation of a dilatant behavior can be suppressed, for example, by the slow addition of the SiO 2 particles to the initially introduced dispersion medium and, at the beginning of the addition, to be stirred very slowly, later towards the end, more rapidly.
  • larger shear forces are to be avoided over the entire dispersion process, since shear forces lead to abrasion on the dispersion device and the friction to a temperature development and thus has a negative influence on the degree of filling.
  • the dispersant is initially charged and the SiO 2 particles are added slowly and preferably continuously.
  • the SiO 2 particles can also be added in several steps (in portions).
  • the pore size and distribution in the shaped bodies produced from the dispersion can be adjusted in a targeted manner.
  • Dispersing devices may be all devices known to the person skilled in the art and devices are used. Preference is also given to devices which contain no metal parts associated with the dispersion in Contact could come to a metal contamination by abrasion to avoid.
  • the dispersion should be carried out at temperatures between 0 ° C and 50 ° C, preferably between 5 ° C and 30 ° C take place.
  • any gases present in the dispersion e.g. Air removed become. This is preferred during and / or after the carried out complete dispersion.
  • the object of the present invention to provide a simple, fast and inexpensive method by which can be prepared from the dispersions of the invention porous and amorphous SiO 2 shaped bodies with extremely high fill levels, not those known from the prior art Disadvantages.
  • step 2 Before transferring the dispersion into a mold (step 2) the dispersion still a pH change by means of mineral Be subjected to acids or bases.
  • Preferred acids are HCl, HF, H 3 PO 4 , H 2 SO 4 or silica, and as bases NH 3 , NaOH and KOH. Particular preference is given to HCl, HF or NH 3 and NaOH, very particularly preferably HF and NH 3 . In this case, a pH of 2-7 or 7-11, preferably 3-5 or 9-10 should be set.
  • the conversion of the dispersion into a mold takes place in a Skilled in the art, such as by pouring into one Shape.
  • Shaping can take place at temperatures from 0 ° C to the boiling point of the Dispersant be carried out. Preference is given to temperatures between 20 ° C and 30 ° C.
  • molds To shape all known to those skilled in the art are suitable as molds To shape. Depending on the desired molded body, molds may be included and be used without a core. Furthermore, the forms can einund be multi-part. Crucible shapes should preferably be at least 1 ° conical to facilitate demolding.
  • materials are in principle all materials, such as They are also commonly used in ceramics.
  • Prefers are materials that have a low adhesion to the dispersion show, such as Plastics, silicones, glass, silica glass or graphite.
  • Particularly preferred are polyethylene (PE), Polypropylene (PP), polytetrafluoroethylene (PTFE), polyamide, Si licon rubber and graphite.
  • PE polyethylene
  • PP Polypropylene
  • PTFE polytetrafluoroethylene
  • polyamide polyamide
  • Si licon rubber Si licon rubber
  • graphite Very particular preference is PTFE and graphite.
  • coated materials such as e.g. with PTFE coated metals are used.
  • the shape should preferably have the smoothest possible surface, e.g. have a polished surface.
  • the mold may be porous or non-porous, gas permeable or gas impermeable be. Preference is given to a gas-permeable form. Furthermore, the shape may be elastic or inelastic.
  • the mold consists of a Foil or a film tube. This type of shape is suitable especially for the production of rods and tubes, as in EP 318100 described.
  • any type of film can be used as the film.
  • the shape of the dispersion withdraws a part of the dispersant.
  • Sludge casting known to those skilled in the art be such. described in DE OS 2218766. This allows the Filling degree of the molded part during molding up to 95 % By weight.
  • a rotationally symmetrical shaped body can also by means of methods of shaping known to the person skilled in the art, such as e.g. Screwing method, roller method or centrifugal casting method, to be obtained.
  • a shaped body also outside and / or inside of a be formed predetermined moldings.
  • anyone can do it methods known to those skilled in the art, e.g. in EP 473104.
  • Silica glass tubes or rods with porous interior and / or exterior areas representable.
  • moldings can also be made in this way made of different layers.
  • step 3) the solidified dispersion becomes more dimensionally stable Molded out of mold.
  • the solidification of the dispersion is temporal depending on the degree of filling, the particle distribution, the temperature and the pH of the dispersion.
  • Preferred temperatures for solidification are temperatures between -196 ° C and the boiling point of the dispersing medium, temperatures between are preferred -76 ° C and 50 ° C, more preferably between -20 ° C and 30 ° C and most preferably between 0 ° C and 30 ° C.
  • solidification into a dimensionally stable shaped body takes place within one minute to 24 hours, preferably times between one minute and six hours are particularly preferred are times between one minute and 30 minutes.
  • a preferred one Mold release agent is e.g. Graphite.
  • step 4 the drying of the obtained from step 3) Molding.
  • the drying takes place by means of the skilled person known methods such as e.g. Vacuum drying, drying by means of hot gases, e.g. Nitrogen or air or contact drying. Also a combination of the individual drying methods is possible. A drying by means of hotter is preferred Gases.
  • Drying takes place at temperatures in the molding between 25 ° C and the boiling point of the dispersant in the pores of the molding.
  • the drying times depend on the volume to be dried Shaped body, the maximum layer thickness, the dispersant and the pore structure of the molded article.
  • the shrinkage depends on the degree of filling of the moist molded body. At a degree of filling of 80% by weight, the volume shrinkage is ⁇ 2.5% and the linear shrinkage ⁇ 0.8%. At higher filling level is the shrinkage is lower.
  • a foreign atom component in particular of metals of ⁇ 300 ppmw, preferably ⁇ 100 ppmw, more preferably ⁇ 10 ppmw and most preferably ⁇ 1 ppmw.
  • the moldings obtainable in this way are an amorphous, open-pore, near-net shape SiO 2 shaped body of any dimensions and shape.
  • the thus obtainable shaped body has a lower anisotropy in density as available in the prior art Moldings.
  • These shaped articles are characterized in that they consist of at least 64% by volume, preferably at least 70% by volume, of round SiO 2 particles which have a bimodal particle size distribution and a pore volume (determined by means of mercury porosimetry) of 1 ml / g 0.01 ml / g, preferably 0.8 ml / g to 0.1 ml / g, more preferably from 0.4 ml / g to 0.1 ml / g and pores having a pore diameter of 1 to 10 microns preferably 3 to 6 microns, which are sinterstabil to 1000 ° C or pores having a bimodal pore diameter distribution, with a maximum of the pore diameter in the range of 0.01 to 0.05 microns, preferably 0.018 to 0.022 microns and a second maximum of the pore diameter in the range of 1 to 5 microns is preferably 1.8 to 2.2 microns.
  • Moldings according to the invention may furthermore have pores with a bimodal pore diameter distribution, with a maximum pore diameter in the range from 0.01 to 0.05 ⁇ m, preferably 0.018 to 0.022 ⁇ m, and a second maximum pore diameter in the range from 1 to 5 ⁇ m, preferably 1.8 to 2.2 microns, wherein the pore diameter distribution on heating changed so that at 1000 ° C is a monomodal pore diameter distribution and the pore diameter in the range of 2.2 to 5.5 microns preferably 3.5 to 4.5 microns and the inner surface of the shaped body is 100 m 2 / g to 0.1 m 2 / g, preferably 50 m 2 / g to 0.1 m 2 / g.
  • the moldings of the invention are up to 1000 ° C. sinter stable with respect to their volume.
  • the use of larger particles in the dispersion causes larger Pores in the molding and a narrow particle size distribution in The dispersion causes a narrow pore size distribution in the shaped body causes.
  • the density of the molding according to the invention is between 1.4 g / cm 3 and 1.8 g / cm 3 .
  • the described moldings with monomodal pore distribution are sinter stable up to 1000 ° C for at least 24h. Further are They are thermally stable and have a very low thermal Expansion factor.
  • the shaped bodies according to the invention preferably have a bending strength of between 0.1 N / mm 2 and 20 N / mm 2 , more preferably between 0.5 and 10 N / mm 2, particularly preferably between 0.8 and 10 N / mm 2 .
  • these moldings show a higher bending strength than green bodies with monomodal particle size distribution as known from the prior art. Further, by heat treatment, increased flexural strength can be achieved.
  • the shaped bodies described can, due to their special Properties are widely used, e.g. as filter materials, Thermal insulation materials, heat shields, catalyst support materials as well as "preform" for glass fibers, optical fibers, serve optical glasses or quartz goods of all kinds.
  • porous Shaped bodies with a wide variety of molecules, substances and substances be wholly or partially offset. Preference is given to molecules, Substances and substances that are catalytically active. there all methods known to the person skilled in the art can be used, as they are e.g. in US 5655046 are described.
  • the open-pore Green body pores in the upper nanometer to lower mycrometer range to, preferably in the range of 0 to 10 microns.
  • the open-pore Green body pores with a bimodal distribution in the bottom Nanometer to lower mycrometer range preferably in the range from 1 to 20 nm and 1 to 10 ⁇ m.
  • the dispersion thus prepared consisted of 890 g of solid, which corresponds to a solids content of 83.96 wt.% (Of which in turn 94.94% fused silica and 5.06% fumed silica).
  • Part of the dispersion was poured into two open topped rectangular molds made of PTFE (5cm * 15cm * 2cm). After 4 hours, the two moldings were demolded by disassembling the mold and dried in a drying oven at 200 ° C. The dried shaped articles had a density of 1.62 g / cm 3 .
  • a molded article was sintered in a high vacuum (10 -5 mbar) by heating at 1620 ° C for one minute at a heating rate of 2 ° C / min.
  • the resulting sintered shaped body had a density of 2.2 g / cm 3 , consisted of 100% amorphous, transparent, gas-impermeable silica glass without gas inclusions and an OH group content below 1 (quantitative determination by means of IR spectroscopy in transmission).
  • the measurable shrinkage over the porous shaped body was based on the volume 26.37%, which is a linear shrinkage of 10%.
  • the second molded body was also heated in a high vacuum (10 -5 mbar) up to 1620 ° C at a heating rate of 2 ° C / min.
  • a high vacuum 10 -5 mbar
  • the density of the shaped body was determined.
  • the thus determined density of the shaped body as a function of the sintering temperature is shown in Table 1. Density of the molding as a function of the sintering temperature. Temperature [° C] Density [g / cm 3 ] 200 1.62 400 1.61 600 1.63 800 1.62 1000 1.63 1200 1.68 1400 1.81 1600 2.20
  • Figure 1 shows a SEM image of the dried at 200 ° C. Molding.
  • Pore volume and inner pore surface of the samples were determined at the temperatures mentioned. The result is shown in Table 2.
  • Pore volume and inner pore surface (by means of mercury porosimetry) sample Pore volume [ml / g] Inner surface [m 2 / g] 200 ° C 0.24 33.23 600 ° C 0.22 33.068 1000 ° C 0.21 27.78 1200 ° C 0.18 8,217 1400 ° C 0.097 2.01
  • the speed of rotation of the stirrer was initially 400 rpm. and gradually became 2000 rpm. elevated. Following complete dispersion, all three dispersions were subjected to a slight vacuum (0.8 bar) for 10 minutes to remove any trapped air bubbles.
  • the dispersions thus prepared consisted of 890 g of solid, which corresponds to a solids content of 83.96 wt.%.
  • the proportion of fumed silica in dispersion was a) 0% by weight, in b) 5.06% by weight and in c) 10.12% by weight.
  • the dispersions were each in 10 open at the top rectangular Molded out of PTFE (5cm * 10cm * 2cm). After 4 hours were the moldings demolded by disassembly of the mold and in one Drying oven dried at 200 ° C. After drying was a portion of the samples still at 800 ° C and 1100 ° C for a Hour tempered.
  • silicon dioxide was in a ball mill milled until a grain distribution in the range of> 0.45 microns to ⁇ 50 microns, with the majority of about 60% between 1 micron and 10 microns.
  • Example 1 a Produce dispersion with a solids content of ⁇ 80% by weight, the dispersion became abrupt at 79% by weight solids firmly. A transfer of the mass into a form was not more is possible.

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EP00965941A 1999-09-09 2000-09-07 HOCHGEFÜLLTE SiO2-DISPERSION, VERFAHREN ZU IHRER HERSTELLUNG UND VERWENDUNG Revoked EP1210294B1 (de)

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DE19943103A DE19943103A1 (de) 1999-09-09 1999-09-09 Hochgefüllte SiO2-Dispersion, Verfahren zu ihrer Herstellung und Verwendung
DE19943103 1999-09-09
PCT/EP2000/008752 WO2001017902A1 (de) 1999-09-09 2000-09-07 HOCHGEFÜLLTE SiO2-DISPERSION, VERFAHREN ZU IHRER HERSTELLUNG UND VERWENDUNG

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ATE295335T1 (de) 2005-05-15
CA2384288A1 (en) 2001-03-15
DE19943103A1 (de) 2001-03-15
ES2240171T3 (es) 2005-10-16
DE50010303D1 (de) 2005-06-16
WO2001017902A1 (de) 2001-03-15
US6699808B1 (en) 2004-03-02
CN1221471C (zh) 2005-10-05
PT1210294E (pt) 2005-08-31
CN1373737A (zh) 2002-10-09
DK1210294T3 (da) 2005-08-15
EP1506947A3 (en) 2005-03-02
EP1210294A1 (de) 2002-06-05
KR100517814B1 (ko) 2005-09-29
KR20020048402A (ko) 2002-06-22
EP1506947A2 (de) 2005-02-16
JP2003508334A (ja) 2003-03-04

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